US4699851A - Solid electrolyte - Google Patents

Solid electrolyte Download PDF

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Publication number
US4699851A
US4699851A US06/910,224 US91022486A US4699851A US 4699851 A US4699851 A US 4699851A US 91022486 A US91022486 A US 91022486A US 4699851 A US4699851 A US 4699851A
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United States
Prior art keywords
solid electrolyte
solid
heteropolyacid
represented
hydrogen
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Expired - Fee Related
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US06/910,224
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English (en)
Inventor
Tetsuichi Kudo
Go Kawamura
Akira Ishikawa
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Hitachi Ltd
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Hitachi Ltd
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Assigned to HITACHI, LTD., A CORP. OF JAPAN reassignment HITACHI, LTD., A CORP. OF JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ISHIKAWA, AKIRA, KAWAMURA, GO, KUDO, TETSUICHI
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a hydrogen ion (generally its hydrate)-conductive solid electrolyte. Particularly, it relates to a solid electrolyte which is suitably used in electrochemical equipment such as hydrogen-oxygen fuel cell, hydrogen sensor or pH sensor.
  • An object of the present invention is to provide a novel solid electrolyte which is suitably used in fuel cells, various sensors, electrochromic display elements or the like.
  • the heteropolyacid containing carbon as a heteroatom to be used in the present invention exhibits a remarkable proton conductivity, that is, it is a proton-conductive solid electrolyte.
  • the heteropolyacid has advantages in that its preparation is simple and that it can be molded more easily than other heteropolyacids. Further, the heteropolyacid is still advantageous in that a firm thin film can be produced from an aqueous solution thereof.
  • a heteropolyacid solid electrolyte is a solid comprising a heteropolyanion represented by the general formula, M' x M y O z m- , and a hydrated proton represented by the general formula, H(m' H 2 O) + , wherein proton is conducted.
  • M is generally tungsten(W) or molybdenum(Mo) and P,Si,As and the like are known as the heteroatom M'.
  • the solid electrolyte according to the present invention is represented by the above formula wherein M' is carbon (C) and is a novel electrolyte which has not been known up to this time.
  • heteropolyacids of the prior art have been prepared by liquid phase reaction between polytungstic acid (or polymolybdic acid) and an acid containing a heteroatom (for example, dodeca acid)
  • the solid electrolyte of the present invention is prepared by the reaction between tungsten carbide and a solution of hydrogen peroxide.
  • the heteropolyacid of the present invention is a solid heteropolyacid containing carbon as a heteroatom
  • M' which comprises a heteropolyanion represented by the general formula, M' x M y O z m - (wherein the ratio of x to y is between 1:12 and 4:12) and a hydrated proton represented by the formula, H(m' H 2 O) + .
  • M' is C and M is at least one element selected from the group consisting of W and Mo.
  • the above formula can be also represented by the formula: WO 3 .aCO 2 .bH 2 O 2 cH 2 O (wherein 0.083 ⁇ a ⁇ 0.25, 0.05 ⁇ b ⁇ 1 and 0.16 ⁇ c ⁇ 4).
  • FIG. 1 shows a cross-sectional view of a cell produced by using a solid electrolyte of the present invention.
  • a cell shown in FIG. 1 was produced by the use of the above solid plate.
  • numeral 1 refers to the above solid plate.
  • Platinum springs 4 and 5 press platinum electrodes 2 and 3 against the both surfaces of the solid plate 1, respectively.
  • the other ends of the springs 4 and 5 are taken out as electric leads 6 and 7.
  • Glass tubes 8 and 9 are bonded to the solid electrolyte 1 with an epoxy adhesive 10.
  • Steam-saturated hydrogen was fed at 10° C. via inlets 11 and 12 and discharged via outlets 13 and 14, respectively.
  • the electromotive force generated between the electric leads 6 and 7 in this step was O V.
  • P H .sbsb.2 is hydrogen concentration of the gas fed via the inlet 12.
  • the resistance of the solid electrolyte was estimated based on the response of the voltage given when a pulse of an electric current was applied on the cell shown in FIG. 1.
  • the resistance was about 500 ⁇ at 20° C. Since the solid electrolyte had a thickness of 0.2 cm and the electrode area was 0.2 cm 2 , the specific resistance was 500 ⁇ cm.
  • a solid electrolyte stock solution was prepared in a similar manner as the one described in Example 1.
  • the stock solution was placed in a flat-bottomed glass vessel. Air of a room temperature (about 20° C.) was blown into the vessel to thereby evaporate the moisture, thus solidifying the solution.
  • the obtained solid plate was amorphous and had a molar ratio of C to W of 1:9. When the solid plate was heated, it began to release CO 2 at a temperature of about 200° C. and decomposed into WO 3 .
  • the other characteristics thereof were similar to those of the solid obtained in Example 1. Accordingly, it was apparent that the solid obtained in Example 2 was a heteropolyacid (solid) containing carbon as a heteroatom.
  • Example 1 A similar cell as the one produced in Example 1 was produced by the use of the above solid plate.
  • the relationship between the electromotive force generated between the leads 6 and 7 and the hydrogen concentration was examined in a similar manner as the one described in Example 1.
  • the concentration dependence represented by the equation 1 was confirmed and the solid was found to be a hydrogen ion-conductive solid electrolyte.
  • the specific resistance of the solid electrolyte was 250 ⁇ cm.
  • Example 2 C molybdenum carbide
  • Mo 2 C molybdenum carbide
  • WC molybdenum carbide
  • the solution was solidified by blowing air to obtain a heteropolyacid having a ratio of C to Mo of about 1:11.
  • a similar cell as the one shown in FIG. 1 was produced by the use of this solid plate.
  • the relationship between the electromotive force generated between the leads 6 and 7 and the hydrogen concentration was examined in a similar manner as the one described in Example 1. As a result of this examination, the concentration dependence represented by the equation 1 was observed.
  • the specific resistance of the solid electrolyte was 300 ⁇ (at 20° C.).
  • Example 2 The same procedure as the one described in Example 1 was repeated except that a mixture comprising WC and MO 2 C at a molar ratio of 18:1 instead of WC was reacted with H 2 O 2 to obtain a solid electrolyte stock solution.
  • the stock solution was placed in a flat-bottomed glass vessel and solidified by blowing air.
  • the obtained solid was a heteropolyacid having a molar ratio of C to metal (W+Mo) of about 1:9.
  • a similar cell as the one shown in FIG. 1 was produced by the use of the above plate.
  • the relationship between the electromotive force generated between the leads 6 and 7 and the hydrogen concentration was examined to observe the concentration dependence represented by the equation 1, thus confirming that the obtained heteropolyacid containing carbon, tungsten and molybdenum was also a hydrogen ion-conductive solid electrolyte.
  • the solid electrolyte had a specific resistance of about 300 ⁇ (at 20° C.).
  • the solid electrolyte of the present invention has excellent effects.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Conductive Materials (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Fuel Cell (AREA)
  • Catalysts (AREA)
US06/910,224 1985-01-25 1986-01-16 Solid electrolyte Expired - Fee Related US4699851A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60010840A JPS61171069A (ja) 1985-01-25 1985-01-25 固体電解質
JP60-10840 1985-01-25

Publications (1)

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US4699851A true US4699851A (en) 1987-10-13

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US06/910,224 Expired - Fee Related US4699851A (en) 1985-01-25 1986-01-16 Solid electrolyte

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US (1) US4699851A (de)
EP (1) EP0211084B1 (de)
JP (1) JPS61171069A (de)
DE (1) DE3685860T2 (de)
WO (1) WO1986004320A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4691786B2 (ja) * 2001-01-15 2011-06-01 トヨタ自動車株式会社 燃料電池電解質膜の高温挙動解析治具および方法
CN106596684A (zh) * 2016-12-01 2017-04-26 深圳市深安旭传感技术有限公司 一种氢气传感器

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50536A (de) * 1973-05-11 1975-01-07

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0610091B2 (ja) * 1984-05-25 1994-02-09 株式会社日立製作所 ヘテロポリ酸及びそれを乾固させて得られる膜を有するエレクトロクロミック表示素子
DE3617945C2 (de) * 1985-05-29 1993-10-28 Hitachi Ltd Verfahren zur Herstellung von Reliefbildern unter Verwendung eines strahlungsempfindlichen Materials mit einem Gehalt an einer Polywolframsäure mit Peroxogruppen und gegebenenfalls Heterokohlenstoffatomen
JPH05189135A (ja) * 1992-01-14 1993-07-30 Canon Inc 座標入力装置

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50536A (de) * 1973-05-11 1975-01-07

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EP0211084B1 (de) 1992-07-01
DE3685860D1 (de) 1992-08-06
EP0211084A4 (de) 1989-09-26
WO1986004320A1 (fr) 1986-07-31
DE3685860T2 (de) 1993-02-25
JPS61171069A (ja) 1986-08-01
EP0211084A1 (de) 1987-02-25

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